Purification method for purifying water in a spent fuel pool in a nuclear power plant

ABSTRACT

A purification method for spent fuel pool water from nuclear power generation, the method comprising: passing the water at a linear flow velocity of 50 m/h or less through a purification apparatus for the water comprising an ion exchange resin layer and a metal-doped resin layer which is laid at a bed height of 2 cm or more on a surface layer of the ion exchange resin layer wherein the water to be treated is contacted with the metal-doped resin layer to decompose a pro-oxidant contained in the water; and subsequently contacting the water with the ion exchange resin.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a division of U.S. patent application Ser. No. 14/520,635 filedon Oct. 22, 2014, which claims priority to Japanese Patent ApplicationNo. 2013-221135 filed on Oct. 24, 2013, which is hereby incorporated byreference in its entirety herein.

FIELD OF THE INVENTION

The present invention relates to a treatment method and apparatus forspent fuel pool water from nuclear power plants, particularly to apurification method and apparatus for decomposing and removingpro-oxidants contained in spent fuel pool water, such as hydrogenperoxide, and a treatment method and apparatus for spent fuel pool waterthat incorporate the purification method and apparatus.

BACKGROUND

To purify spent fuel pool water from nuclear power plants and recyclethe purified water as cooling water for spent fuel rods, a demineralizerusing a granular ion exchange resin is placed as a purification devicefor fuel pool water. This demineralizer is placed to inhibit corrosionof stored spent fuels and various materials and remove radioactivesubstances from pool water, thus maintaining long-term soundness, suchas decreased radiation exposure of operators.

In the demineralizer, it is necessary to replace ion exchange resinshaving degraded performance by fresh resins. In this case, since avolume of spent ion exchange resins are generated as a radioactivewaste, the replacement costs money for the new ion exchange resins aswell as money for disposal of the radioactive waste and requires a placefor the disposal. For these reasons, it has been desired to prolong thelives of ion exchange resins.

However, spent fuel pool water that is obtained from a nuclear powerplant such as a pressurized-water reactor (PWR) contains pro-oxidantssuch as hydrogen peroxide which is generated by decomposition of thewater subjected to radiation from fuel rods and hydroperoxyl radicalsand hydroxyl radicals which are generated from hydrogen peroxide(hereinafter, these pro-oxidants are referred to as “pro-oxidants”) andboron which is derived from boric acid added for control of nuclearfission reaction of fuels. In general, spent fuel pool water containshydrogen peroxide in the order of a few or several ppm and boron in aconcentration of about 2000 to about 3000 ppm. Such spent fuel water istreated directly by ion exchange in a purification apparatus for fuelpool water. However, a demineralizer using a granular ion exchangeresins cannot remove those pro-oxidants. Hence, the pro-oxidants remainin fuel pool water, waste storage bunker water, and condensate storagewater that is recovered after purification of fuel pool water or wastestorage bunker water and then stored. In addition, since thepro-oxidants have a very strong oxidizing action, they oxidize cationresins in ion exchange resins and elute polystyrene sulfonic acid (PSS).The eluted PSS is attached to anion exchange resins and decreases theirreaction rate. Further, hydrogen peroxide oxidizes and degrades cationexchange resins and, in consequence, sulfate ions and the like areeluted from the cation exchange resins and increase the electricconductivity at an outlet of an ion exchange resins column. The strongoxidizing action of the pro-oxidants contributes to corrosion of steelmaterials such as pipes and tanks.

It is believed that the main cause of the degradation of ion exchangeresins is oxidation of cation exchange resins that is caused by theircontact with pro-oxidants contained in such water. To solve thisproblem, the following methods have been proposed: a method of alkalinedecomposition of pro-oxidant by contacting water containing thepro-oxidant with anion exchange resins before contacting the water withcation exchange resins (Patent Document 1: Japanese Patent PublicationNo. 2000-002787), a method of removing pro-oxidant by contacting it withgranular active carbon and a method of removing pro-oxidant bycontacting it with ion exchange resins on which platinum group catalystparticles are doped (Patent Document 2: Japanese Patent Publication No.H10-111387), a method of removing pro-oxidant by passing watercontaining the pro-oxidant through a platinum catalyst coated membrane(Patent Document 3: Japanese Patent Publication No. 2003-156589), amethod of removing pro-oxidants by contacting them with active carbon toadsorb them (Patent Document 4: Japanese Patent Publication No.2008-232773), and a method of removing pro-oxidants by passing watercontaining the pro-oxidants through a manganese filter (Patent Document5: Japanese Patent Application No. 2012-217133). However, these methodsproposed so far relate to purification of water having a low pro-oxidantconcentration of about 0.01 to about 0.001 mg/L, such as nuclear reactorcooling water or radioactive waste water, and there are no examples ofapplication of those methods to purification of spent fuel pool watercontaining pro-oxidants in a high concentration of 1 mg/L or more aswell as boric acid (for example, about 2000 to about 3000 mg/L).

SUMMARY

The present invention aims to reduce pro-oxidants contained in spentfuel pool water from nuclear power plants, especially frompressurized-water reactor (PWR), prolong the life of ion exchange resinsin a purification apparatus for fuel pool water, and lower the frequencyof replacement of the ion exchange resins.

According to the present invention, there is provided a technique forwater treatment at nuclear power plants of pressurized-water reactor(PWR); in the technique, before ion exchange resins are used todemineralize water to be treated that contains pro-oxidants (e.g.,hydrogen peroxide) generated by radiolysis of spent fuel pool water fromthe nuclear power plants of PWR, the water to be treated is contactedwith particular metal-doped resins to reduce the pro-oxidants containedin the water, decrease load placed on a demineralizer and maintain thehigh purity of the treated water as well as prolong the life of the ionexchange resins and reduce generation of spent ion exchange resins thatare radioactive secondary wastes.

More specifically, the present invention includes the followingembodiments:

[1] A purification method for spent fuel pool water from nuclear powergeneration, the method comprising: passing the water at a linear flowvelocity of about 50 m/h or less through a purification apparatus forthe water comprising an ion exchange resin layer and a metal-doped resinlayer which is laid at a bed height of about 2 cm or more on a surfacelayer of the ion exchange resin layer wherein the water to be treated iscontacted with the metal-doped resin layer to decompose a pro-oxidantcontained in the water; and subsequently contacting the water with theion exchange resins.[2] The purification method according to [1], wherein the metal in themetal-doped resin layer is selected from fine particles of palladium,platinum, manganese, iron, and titanium.[3] The purification method according to [1] or [2], wherein thepro-oxidant is hydrogen peroxide, a hydroperoxyl radical, or a hydroxylradical.[4] A treatment method for spent fuel pool water from nuclear powergeneration, the method comprising: purifying the water to be treatedwith a purification apparatus for the water by the purification methodaccording to any one of[1] to [3]; and then recycling the purified waterto the spent fuel pool to use the water.[5] A purification apparatus for spent fuel pool water from nuclearpower generation, comprising an ion exchange resin layer and ametal-doped resin layer which is laid at a bed height of about 2 cm ormore on a surface layer of the ion exchange resin layer.[6] A treatment apparatus for spent fuel pool water from nuclear powergeneration, comprising:

a spent fuel pool at a nuclear power plant;

a purification apparatus for the water, comprising an ion exchange resinlayer and a metal-doped resin layer which is laid at a bed height ofabout 2 cm or more on a surface layer of the ion exchange resin layer;

a delivery line for delivering the water from the spent fuel pool to thepurification apparatus; and

a spent fuel pool water circulation line for returning the waterpurified with the purification apparatus to the spent fuel pool.

Advantageous Effects

By using the treatment method and apparatus of the present invention fortreating spent fuel pool water from nuclear power plants, pro-oxidants(e.g., hydrogen peroxide) generated by radiolysis of the water withradiation from spent fuels can be decomposed efficiently. Hence, thetreatment method and apparatus can prevent oxidative degradation of ionexchange resins filled in a demineralizer and maintain the high purityof the treated water as well as prolong the life of the ion exchangeresins and reduce generation of spent ion exchange resins that areradioactive secondary wastes. For treatment of spent fuel pool waterfrom nuclear power plants of PWR, it is an important object to reducethe volume of radioactive secondary wastes, and the present inventionthat can accomplish those achievements is significant.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic flow diagram of a water treatment apparatus of thepresent invention for treating spent fuel pool water from a nuclearpower plant.

FIG. 2 is a graph showing treatment results of Example 1.

FIG. 3 is a graph showing treatment results of Example 2.

FIG. 4 is a graph showing treatment results of Example 3.

PREFERRED EMBODIMENTS

The present invention is described below with reference to the attacheddrawings, but they are not intended to limit the scope of the invention.

FIG. 1 outlines a flow in a water treatment apparatus of the presentinvention for treating spent fuel pool water that is obtained from anuclear power plant. A spent fuel pool 1 is filled with cooling waterfor cooling storage of a spent fuel rod that is removed from a nuclearreactor (This cooling water is also referred to as “spent fuel poolwater”). Since the spent fuel rod that is removed from a nuclear reactorcontinues emitting radiation even while being stored in fuel pool water,the spent fuel pool water is decomposed by the radiation to generatehydrogen peroxide, hydroxyl radicals or hydroperoxyl radicals. The spentfuel pool water (water to be treated) that is removed from the spentfuel pool 1 (a storage tank for the water to be treated) is transferredvia a transfer pump 2 to a fuel pool purification device 3. The fuelpool purification device 3 comprises an ion exchange resin layer 3 a inwhich ion exchange resins are filled and a metal-doped resin layer 3 bin which metal-doped resins are filled at a bed height of about 2 cm ormore, preferably 5 cm or more, on a surface layer of the ion exchangeresin layer 3 a. When the bed height is less than about 2 cm,pro-oxidants are not well decomposed. The upper limit of the bed heightof the metal-doped resin layer 3 b is not particularly limited; however,since a bed height exceeding about 10 cm results in the decreases of theflow velocity and the volume of the treated water, an appropriate bedheight should be determined. The pro-oxidants contained in the spentfuel pool water are decomposed when passing through the metal-dopedresin layer 3 b. Subsequently, impurity ions are removed through the ionexchange resin layer 3 a. The demineralized water is recycled to thespent fuel pool 1 as cooling water. The flow volume of water to betreated through the demineralizer 3 is based on a linear flow velocityof about 10 to about 50 m/h. When the linear flow velocity is less thanabout 10 m/h, the volume of the circulated water is decreased and itscooling effect on the spent fuel rod is diminished. When the linear flowvelocity exceeds about 50 m/h, the efficiency of contact of thepro-oxidants with the metal-doped resin is reduced and its capability todecompose the pro-oxidants is diminished.

The ion exchange resin used in the present invention may be a common ionexchange resin that is used in purification apparatuses for spent fuelpool water from nuclear power plants, and is preferably a mixed bedanion and cation exchange resin. For example, a mixed bed ion exchangeresin (SNM1, a product of Mitsubishi Chemical Corp.) is suitable.

The metal-doped resin used in the present invention is preferably astrongly basic gel-type spherical resin formed of a polymer resin onwhich metal particles selected from palladium, platinum, manganese, ironand titanium fine particles are doped.

EXAMPLES

The present invention is described below in more detail by means ofexamples.

Example 1

A metal-doped resin was used to examine its capability to decomposehydrogen peroxide in an immersion test.

The metal-doped resin was the Pd-doped resin Lewatit (registeredtrademark) K7333, a product of Lanxess. To a 200 ml beaker, 100 ml of asolution to be treated (Sample 1) containing H₂O₂ in a concentration of20 mg/L and boric acid dissolved in a concentration of 2800 mg/L (as B)was added, 1 ml of the Pd-doped resin was added, and the hydrogenperoxide concentration was determined with time. These hydrogen peroxideand boron concentrations were applied to simulate the quality of fuelpool water that is obtained from a pressurized-water reactor (PWR)nuclear power plant. For reference, the same test was conducted with aboric acid-free solution, i.e., water containing only hydrogen peroxide(This solution is referred to as Sample 2). The hydrogen peroxideconcentration was calculated based on absorbance measured at awavelength of 350 nm with a spectrophotometer by iodometry (AtomicEnergy Society of Japan: PWR Standard Chemical Analysis 2006). Theresults are shown in Table 1 and FIG. 2.

TABLE 1 Conc. (mg/L) Immersion of hydrogen peroxide time (min) ControlSample 2 Sample 1 0 19.4 19.4 19.4 60 19.4 12.1 12.0 120 19.5 10.8 10.5180 19.6 9.5 9.8 240 19.5 8.8 9.0

FIG. 2 shows that the Pd-doped resin had such a high capability todecompose hydrogen peroxide that about 50% or more of contained hydrogenperoxide was decomposed at about 2 hours after the start of immersion.The influence of contained boric acid on the capability to decomposehydrogen peroxide was not observed.

Example 2

A metal-doped resin was used to examine its capability to decomposehydrogen peroxide in a test in which hydrogen peroxide-containing waterwas passed through a column.

The metal-doped resin, which was the Pd-doped resin Lewatit (registeredtrademark) K7333, a product of Lanxess, was filled at a bed height ofabout 1 to about 10 cm in a glass column with an inside diameter ofabout 16 mm. An untreated water comprising H₂O₂ adjusted to about 2 mg/Lwas passed through the column at a linear velocity LV of about 10 toabout 70 m/h to examine the hydrogen peroxide removing performance ofthe metal-doped resin. The results are shown in Table 2 and FIG. 3.

TABLE 2 Hydrogen peroxide decomposition Linear flow rate (%) by bedheight velocity (m/h) 1 cm 2 cm 5 cm 10 cm 1 95 95 95 95 10 80 95 95 9530 50 95 95 95 50 10 90 93 95 70 2 60 80 90

FIG. 3 shows that about 90% or more of hydrogen peroxide can bedecomposed at a bed height of about 2 cm or more and an LV of about 50m/h or less.

Example 3

The influence of hydrogen peroxide on degradation of ion exchange resinwas examined.

Cation resins of the same type were respectively immersed in solutionshaving various hydrogen peroxide concentrations for 24 hours and thetotal organic carbon (TOC) concentrations were measured with TOC-V, aproduct of Shimadzu Corp. As shown in FIG. 4, it was confirmed thathydrogen peroxide contained in a concentration of less than about 1 ppmhad little influence on resin degradation. Hence, it is adequate todecompose 90% or more of hydrogen peroxide present in the order of a fewor several ppm in fuel pool.

In general, ion exchange resins are replaced by fresh resins in a TOCconcentration of more than about 20 ppm. FIG. 4 shows that when thehydrogen peroxide concentration exceeds about 3.5 ppm, the TOCconcentration exceeds about 20 ppm and replacement of ion exchange resinis required. FIGS. 2 and 4 show that untreated water (hydrogen peroxideconcentration: 20 ppm) has such a high hydrogen peroxide concentrationas to require replacement of ion exchange resin after the water ispassed through the resin once, whereas the treatment method of thepresent invention achieves the hydrogen peroxide decomposition rate ofabout 95%, decreases the hydrogen peroxide concentration of water to betreated through an ion exchange resin to about 1 ppm or less, andconsiderably lowers the frequency of replacement of the ion exchangeresins.

INDUSTRIAL APPLICABILITY

Before an ion exchange resin is used to demineralize water to be treatedthat contains pro-oxidants (e.g., hydrogen peroxide) generated byradiolysis of spent fuel pool water from nuclear power plants of PWR, itis possible according to the present invention to reduce thepro-oxidants contained in the water to be treated, decrease load placedon a demineralizer and maintain the high purity of the treated water aswell as prolong the life of the ion exchange resins and reducegeneration of spent ion exchange resins that are radioactive secondarywastes. Accordingly, the present invention is significant.

What is claimed is:
 1. A purification apparatus for water in a spentfuel pool in a nuclear power plant, comprising: a spent fuel poolcontaining a spent fuel from a nuclear power plant and water; an ionexchange resin layer having an inlet side and an outlet side; ametal-doped resin layer laid at a bed height of from about 2 cm or moreto about 10 cm or less on the surface of the inlet side of the ionexchange resin layer; and a delivery line configured to deliver thewater from the spent fuel pool to the metal-doped resin layer.
 2. Thepurification apparatus according to claim 1 further comprising a spentfuel pool water circulation line configured to return the water from theion exchange layer to the spent fuel pool.
 3. The purification apparatusaccording to claim 1, wherein the water from the spent fuel poolcomprises peroxide, and wherein 90% or more of the peroxide isdecomposed by passing the water through the metal-doped resin layer andthe ion exchange resin layer.
 4. The purification apparatus according toclaim 1, wherein the metal in the metal-doped resin layer is selectedfrom the group consisting of fine particles of palladium, platinum,manganese, iron, and titanium.
 5. The purification apparatus accordingto claim 1, wherein the water from the spent fuel pool further comprisesa hydroperoxyl radical, a hydroxyl radial, or combination thereof. 6.The purification apparatus according to claim 1, wherein the deliveryline is further configured to deliver the water so that the water passesthrough the ion exchange resin layer at a linear flow velocity of from30 m/h or more to about 50 m/h or less during operation.